US9745250B2 - Process to crystallize chelating agents - Google Patents

Process to crystallize chelating agents Download PDF

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Publication number
US9745250B2
US9745250B2 US15/309,516 US201515309516A US9745250B2 US 9745250 B2 US9745250 B2 US 9745250B2 US 201515309516 A US201515309516 A US 201515309516A US 9745250 B2 US9745250 B2 US 9745250B2
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seeds
glda
chelating agent
dispersion
mgda
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US20170158613A1 (en
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Elwin Schomaker
Paulus Johannes Cornelis Van Haeren
Martin Heus
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Nouryon Chemicals International BV
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Akzo Nobel Chemicals International BV
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Assigned to AKZO NOBEL CHEMICALS INTERNATIONAL B.V. reassignment AKZO NOBEL CHEMICALS INTERNATIONAL B.V. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HEUS, MARTIN, VAN HAEREN, Paulus Johannes Cornelis, SCHOMAKER, ELWIN
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Assigned to WILMINGTON TRUST (LONDON) LIMITED, AS COLLATERAL AGENT reassignment WILMINGTON TRUST (LONDON) LIMITED, AS COLLATERAL AGENT SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AKZO NOBEL CHEMICALS B.V., AKZO NOBEL CHEMICALS INTERNATIONAL B.V., AKZO NOBEL SURFACE CHEMISTRY LLC, STARFRUIT US MERGER SUB 1 LLC, STARFRUIT US MERGER SUB 2 LLC
Assigned to NOURYON CHEMICALS INTERNATIONAL B.V. reassignment NOURYON CHEMICALS INTERNATIONAL B.V. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: AKZO NOBEL CHEMICALS INTERNATIONAL B.V.
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/38—Separation; Purification; Stabilisation; Use of additives
    • C07C227/40—Separation; Purification
    • C07C227/42—Crystallisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D9/00—Crystallisation
    • B01D9/0004—Crystallisation cooling by heat exchange
    • B01D9/0013—Crystallisation cooling by heat exchange by indirect heat exchange
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D9/00—Crystallisation
    • B01D9/0036—Crystallisation on to a bed of product crystals; Seeding

Definitions

  • the present invention relates to a process to crystallize chelating agents.
  • the detergent market is currently undergoing important changes. Due to ecological and regulatory reasons the use of phosphate in high concentrations in detergent formulations is to be banned altogether or must at least be greatly reduced.
  • the formulators of detergent products have to find alternatives to replace the phosphate compounds, with the most promising replacements being the more easily biodegradable chelating agents, such as aspartic acid N,N diacetic acid and it salts (ASDA), methylglycine N,N-diacetic acid and its salts (MGDA) and glutamic acid N,N-diacetic acid and its salts (GLDA).
  • ASDA aspartic acid N,N diacetic acid and it salts
  • MGDA methylglycine N,N-diacetic acid and its salts
  • GLDA glutamic acid N,N-diacetic acid and its salts
  • Such chelating agents tend to be readily available and are used in a concentration from 5% to 60%.
  • Many detergent formulations contain co-builders, which are typically polymers or
  • solid raw materials are required by the formulator.
  • the raw materials in automatic dishwashing (ADW) applications the raw materials have to be in powder, and preferably granule, form to improve the tabletting and solids handling of the formulation.
  • Powders or granules typically have a size comprised between 50 and 3,000 microns.
  • the powder or granules of many chelating agents when obtained in the amorphous state, show hygroscopic properties, which is unacceptable for the ADW formulators.
  • the hygroscopic properties render the material sticky, thus introducing storage, handling and manufacturing problems.
  • Flow properties of particles are critical in many ways. During manufacture of the particles themselves, they must flow smoothly relative to one another.
  • US20120046491 discloses the preparation of a powder comprising one or more derivatives of glutamine-N,N-diacetic acid or glycine-N,N-diacetic acid with a degree of crystallinity of 30%, the process comprising concentrating an aqueous solution to obtain a crystal slurry, wherein one concentration range is from 20% to 60% by weight (starting material), based on the total weight of the crystal slurry, and ripening the crystal slurry in a paste bunker and then in a thin-film contact dryer, wherein the residence time in the paste bunker (seeds: fine powder up to 50% of total weight) and in the thin-film contact dryer is in total 15 minutes and the concentration occurs in an evaporator with rotating internals which are arranged at a distance relative to an inside wall of the evaporator of 1% of the diameter of the evaporator (high shear rate in the liquid film on the inside wall).
  • Temperature ranges for the first process step are between 50° C.-140° C. and preferably between 80° C.-110° C., and pressure ranges are between 0.1 and 4 bar, preferably between 0.8 and 1.2 bar.
  • Ripening is carried out for at least 15 minutes and up to 3 hours and thin-film treatment is carried out for between 0.5 minutes and 20 minutes from 60° C. up to 140° C.
  • a powder is obtained which predominantly has the crystal modification of the monohydrate or the dihydrate of MGDA (methylglycine diacetic acid). The complicated process appears to be specifically designed for trisodium MGDA.
  • US20120149936 discloses a process for preparing crystalline solids of glycine-N,N-diacetic acid derivatives of sufficiently low hygroscopicity by introducing one crystalline compound as a seed; a spray granulation is carried out, which may be followed by a heat treatment step to increase the crystallinity. Only glycine-N,N-diacetic acid derivatives are mentioned in the document.
  • DE 42 11 713 discloses a process to prepare the chelating agents GLDA and ASDA (aspartic acid N,N-diacetic acid). Though it is suggested in general that the materials could be isolated by several methods, one of which is crystallization, all the examples deal with depositing ASDA in the amorphous form.
  • U.S. Pat. No. 5,981,798 discloses the preparation of a crystalline solid of a glycine N—N-diacetic acid derivative.
  • a concentrated solution of the trisodium salt of MGDA methylglycine N,N-diacetic acid
  • the glycine N,N diacetic acid derivatives, such as the trisodium salt of MGDA are crystallized under mechanical stress.
  • mechanical stress said to come from a mixing, stirring, kneading or extrusion apparatus, should be understood to mean the application of low shear conditions such as rotation of 20 rpm.
  • the present invention now provides a process to crystallize a chelating agent containing a first step of adding seeds to a saturated or supersaturated aqueous solution or dispersion of the chelating agent and a second step of milling the dispersion, and the product obtainable by the process.
  • the process proved to be much more efficient than the state of the art processes in the sense that it is not only faster but in many instances also provides a better particle size distribution with less extremely small particles.
  • the crystals prepared in accordance with the present invention were found to be of an improved morphology, were more free flowable even at high humidity, and it was found possible to make tablets from them, given that they have an increased strength and yet a good dissolution rate.
  • the process of the invention is favourable as no mother liquor waste stream is created, in contrast with traditional crystallization processes.
  • the step of milling the dispersion is done using equipment operating at at least 1,000 rpm, more preferably at at least 10,000 rpm.
  • the seeds used in the process of the invention are seeds of a chelating agent, more preferably seeds of the same chelating agent that is in the solution or dispersion and crystallized therefrom.
  • heterogeneous nucleation using seeds of another material than the material crystallized in the process is a process known in the art as heterogeneous nucleation. Heterogeneous nucleation can be much faster than homogeneous nucleation, but the disadvantage is that a less pure product is obtained.
  • the process of the invention contains an additional third step in which the material is at least partly dried, and optionally the material obtained from the third step is crushed or milled and sieved (to collect fractions of the right dimension), extruded, compressed, tableted or processed in any other way to be converted into the solid form that is desired.
  • Drying the material can for example be done by drying droplets or a thin film of the milled, seeded dispersion in an oven and is preferably done at a temperature of between 25 and 100° C.
  • the chelating agent is methylglycine N,N-diacetic acid or a salt thereof (MGDA), glutamic acid N,N-diacetic acid or a salt thereof (GLDA), aspartic acid N,N diacetic acid or a salt thereof (ASDA), more preferably it is GLDA or MGDA.
  • MGDA methylglycine N,N-diacetic acid or a salt thereof
  • GLDA glutamic acid N,N-diacetic acid or a salt thereof
  • ASDA aspartic acid N,N diacetic acid or a salt thereof
  • the chelating agent is GLDA, even more preferably it is partly acidified or fully acidified GLDA (wherein part or all of the countercations are protons).
  • Dissolvine GL-47-S (a 47 wt % solution of L-GLDA tetrasodium salt in water), ex Akzo Nobel Functional Chemicals LLC, Chicago Ill., USA.
  • the Topas software package from Bruker was used for the diffractograms.
  • BPM Bi-Polar Membranes
  • the experimental set-up consisted of three vessels to recycle fluids through the BPM unit.
  • the temperature was controlled by applying heating/cooling to the jacketed reactors.
  • the acid reactor was a 1 l stirred glass reactor and the base and electrolyte loop both used 1.5 l glass reactors without stirring. Nitrogen was passed through the electrolyte solution via a gas sparger in order to dilute the hydrogen gas produced at the cathode to far below the explosion limit.
  • the reactor was charged with a c. 42 wt % GLDA-Na4 solution and the recirculation of the reactor content over the BPM stack was started. Once the GLDA solution was heated to 40° C., an electric current was applied. The voltage (V) over the stack was limited to 25V and the electric current (I) was controlled manually to a maximum of 15 A. When the desired pH was reached, the current to the BPM was minimized and both the reactor and BPM contents were collected.
  • the acidified GLDA solution was established to be a 44 wt % solution of GLDA having a pH of about 2.5.
  • the resulting 44.1 wt % L-GLDA aqueous solution with pH 2.5 (which corresponds to a solution containing about 1 equivalent of sodium cation per GLDA anion) were submitted to a heat treatment for 174 hours at approx. 100° C. to provide for racemization.
  • the obtained D,L-GLDA-NaH3 solution was concentrated to a 50.2 wt % (50:50) L,D-GLDA-NaH3 aqueous solution in a rotavapor, water bath temperature 70° C. and reduced pressure (20 mbar).
  • the crystal slurry was centrifuged in a horizontal Rousselet drum centrifuge to separate the mother liquor from the crystalline product.
  • a sample was prepared having the composition as described in Example 2. To the sample were added needle-shaped seeds having dimensions of 50-100 ⁇ m by 5-10 ⁇ m (identical to the ones described in Example 2). Next, the dispersion of the seeds in the solution was stirred using a spatula for about 1 minute.
  • Example 2 The material from Example 2, using the Ultra Turrax, peaked exothermically at 57° C., while for the solid obtained in Comparative Example 3 without the Ultra Turrax treatment the mixture showed a peak maximum at 70° C., which shows that the material made with the process according to the present invention crystallizes faster than material made using a state of the art process.
  • the resulting mixture was applied as a thick film ( ⁇ 2.5 mm) on a polypropylene substrate and was allowed to dry at 80° C. in an oven.
  • the resulting product could be easily broken and sieved applying a Frewitt sieve, without any difficulties concerning sieve fouling. 75% of the materials were within the specifications set (0.5-1.6 mm).
  • Example 2 The resulting powders of Example 2 (various sieve fractions: ⁇ 0.5; 0.5-0.71; 0.71-1; 1-1.6 mm) all showed free flowing behaviour even after storage at 40° C. at 75% relative humidity (RH) during 70 hrs, despite the fact that the powders showed moisture uptake up to 10%.
  • the moisture content of the product measured using an infrared drying balance at 120° C. was about 8-12%, depending on relative humidity.
  • the crystallinity of the sample was 49% according to XRD.
  • Example 2 The same procedure as described in Example 2 was repeated, but now the resulting mixture was divided into four fractions; two fractions were applied as thick films of ⁇ 2.5 mm and the two other fractions were partly applied as separate droplets of about 2-2.5 mm and in both cases one was allowed to dry at 80° C. and the other at room temperature.
  • Example 4 The dried films were subsequently broken and sieved as described in Example 4. Both the sieving fractions and the granules (dried droplets) were stored at 40° C. at 75% relative humidity during 44 hrs. All samples showed free flowing behaviour, despite the fact that their final moisture contents were in between 11-13 w %.
  • samples were prepared differing in GLDA concentration and seed content.
  • the resulting mixture was applied as a thick film ( ⁇ 2.5 mm) on a polypropylene substrate and was allowed to dry at 80° C. in an oven.
  • the crystallinity of the product was 41% according to XRD
  • the resulting product could easily be broken and sieved, without any difficulties concerning sieve fouling.
  • the sieve recovery of the fraction sized 0.71-2 mm was 70%.
  • Trilon M granulate of BASF as used for seeding in Example 7, was subjected to the same storage conditions as the sample obtained by the process of Example 7. It was concluded that the free flowability performance of the product of the invention was at least similar.
  • the crystallinity of the resulting product was 45% according to XRD.
  • the crystallinity of the resulting product was 38% according to XRD.
  • ASDA-Na4 48 grams of aqueous solution ASDA-Na4 (36 wt %) were weighed into a beaker. Added were 2 grams of ASDA-Na4-containing material obtained by centrifuging off a precipitate that was formed during storage of a concentrated solution, having a crystallinity of 15%, according to XRD.
  • the resulting mixture was applied as a thick film ( ⁇ 2.5 mm) on a polypropylene substrate and was allowed to dry at 80° C. in an oven.
  • the resulting product was powdered and analyzed using XRD, showing a crystallinity of 22%.
  • This material was used as seeding material for a subsequent experiment, following the same procedure as described above.
  • the resulting product was powdered and analyzed using XRD, now showing a crystallinity of 29%.
  • a sieving fraction of 0.71-2 mm was dried at 50° C. under vacuum overnight, prior to flow ability and moisture uptake testing. Up to 3 hrs at 16° C. at 60% relative humidity, the sample remained free flowing, showing a moisture uptake of only 12%.
  • Example 7 The process as described in Example 7 was used to prepare a series of products, using Trilon M Liquid that was concentrated to 50 w %.
  • the particle size characteristics were measured by dynamic image analyzing, according to NEN-ISO 13322-2, using a Sympatec system, from which also the specific surface area was calculated using a density of 1.72 g/ml, as measured using He-pycnometry.
  • Sample dissolution rates of the products were determined in water at room temperature by monitoring the conductivity of the aqueous solution on addition of a fixed amount of MGDA granules.
  • Trilon M Granules reference sample showed some agglomeration after storage for 6 hours at 40° C. at RH 75%, despite the fact that this reference sample showed lower moisture uptake values as compared to the samples according to the invention

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Detergent Compositions (AREA)
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EP14168184.1 2014-05-13
EP14168184 2014-05-13
EP14168184 2014-05-13
PCT/EP2015/060272 WO2015173157A2 (en) 2014-05-13 2015-05-11 Process to crystallize chelating agents

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JP (1) JP6426758B2 (zh)
CN (1) CN106458851B (zh)
CA (1) CA2947459A1 (zh)
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EP3472294B1 (en) * 2016-06-20 2020-07-22 Basf Se Powders and granules and process for making such powders and granules
RU2019129794A (ru) * 2017-02-24 2021-03-25 Басф Се Способ получения твердой соли щелочного металла метилглициндиацетата (mgda) и твердые частицы
EP3649103B1 (en) 2017-07-07 2022-03-30 Nouryon Chemicals International B.V. Process to prepare a solid composition of an amino acid diacetic acid
EP3649105B1 (en) * 2017-07-07 2021-09-01 Nouryon Chemicals International B.V. Sodium methyl glycine-n,n-diacetic acid compound, process to prepare it and use thereof
CN107814734A (zh) * 2017-10-17 2018-03-20 山东泰和水处理科技股份有限公司 绿色螯合剂天冬氨酸二乙酸四钠的制备方法
CN113382980B (zh) * 2018-12-21 2024-06-21 诺力昂化学品国际有限公司 甲基甘氨酸n,n-二乙酸的易碎相组合物
MX2022010260A (es) * 2020-02-20 2022-09-19 Basf Se Proceso para elaborar sales de metal alcalino de metilglicindiacetato solido.
WO2021255525A1 (en) 2020-06-19 2021-12-23 Nouryon Chemicals International B.V. Process to prepare a co granule of methylglycine n,n diacetic acid salts employing a crumbly phase composition of methylglycine n,n diacetic acid salts
CN113444008B (zh) * 2021-06-24 2022-07-12 河北诚信集团有限公司 一种甲基甘氨酸二乙酸三钠盐的分离纯化方法

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CN201832438U (zh) 2010-10-19 2011-05-18 秦贯丰 结晶洗涤分离柱
WO2013096122A1 (en) 2011-12-22 2013-06-27 Dow Global Technologies Llc Process and apparatus for forced circulation evaporative crystallization with large deposit inventory
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US20170158613A1 (en) 2017-06-08
EP3143001A2 (en) 2017-03-22
CN106458851A (zh) 2017-02-22
EP3143001B1 (en) 2018-07-18
WO2015173157A3 (en) 2016-01-07
CN106458851B (zh) 2019-01-11
WO2015173157A2 (en) 2015-11-19
CA2947459A1 (en) 2015-11-19
JP6426758B2 (ja) 2018-11-21
JP2017522168A (ja) 2017-08-10

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